Stabilization of tetra alkyl lead and compositions containing the same



Patented flee.

ST-ES AENT OFFIQE,

WILLIAM S. CALCOTT, OF PENNS GBO VK AND. ALFRED E. PARMELEE, 0F CABNEYS POINT, NEWJERSEY, AS$IGNOES TO B. I. DU PON'I DE NEMO'UBS & COMPANY, OF

WILMINGTON, DELAWARE, A. CORATION OF DELAWARE STABILIZATION 0F TE'IRA ALKYL LEAD AND GOHPOSI'IIONS COIITAINING THE SAME E0 Drawln g.

e terials as hydrocarbons and halo en derivatives of hydrocarbons. More particularly our invention relates to the stabilization of tetra ethyl lead and mixtures containing tetra ethyl lead by the incorporation therewith of smallamounts of di aryl amines or of certain derivatives of di aryl amines.

Ordinar commercial tetra alkyllead, and tetra ethyl lead, decomposes 't i 0S1 Ion s ethylene dibromlde, and 5 grams; of mono particular y slowly on standing, and this decom accelerated when these compoun s in addition such organic substances as halogen derivatives of hydrocarbons. We have discovered that this decomposition can be very materially retarded. or --prevented by the introduction of di a l amines or derivatives of diarylamineasuc for exam le, as the monoand di-hydroxy, alkoxy, an amino substituted diaryl amines. The class of compounds which we have found to be effective for the stabilization of tetra ethyl lead may be re resented by the general formula X -R -'-N -,R X wherein R and R are aromatic hydrocarbon nuclei whichmay be alike or different and X and K are hydrox alkoxy, amino, or hydrogen. In order to isclose the invention in detail, the following examples of actual embodiments thereof are presented' It is tobe understood, however, that these examples are furnished purely for purposes of illustration and that it is not the intention that the invention is to be limited to the paricular reagents, proportions or other conditions therein specified.

Ewample 1 Example 2 To 100 grams of tetra ethyl lead is added,-

with stirring, 0.1 gram of diphenylamine.

contain ample, with 0.5%

7 pounds which Application filed October 81, less. Serial no. 493,907.

Ewampl 3 To 100 grams of tetra methyl lead is added, with stirring, 0.05 gram of p-hydroxy diphenylamine. v

Ewample 4 One hundred grams tetraphenyl lead are mixed with 90 grams ethylene dibromide and 0.2 gram diethoxy diphenylamine,

mmoO-nn-O-omm Ewample 5 Fifty grams of tetra ethyl lead, 45 grams of chlor na hthalene are combined. To this composition is I added p-amino diphenylamine,

J O O in amountsup to one gram.

Fifty grams of tetra ethyl lead, 45 grams of ethylene dibromide, and 5 chlor na hthalene are com ined.. Tothis composition is added 2 4 diamino 4 hydroxy' di henylamine in amountsup to one gram;

he foregoin compositions will be found ems of mono remarkabl sta le against decomposition as evidenced y the fact that they remain free from insoluble matter for long periods of time or the formation ofany insoluble precipitate will be greatly vreduced. For exphenyl-a-naphthylamine samples of tetra et yl .lead hare remained stable and free from sediment for eight months, which otherwise would deeom, ose. giving rise-to a substantial precipitate in t ree to four days or less.

ile henyl-alpha-naphth lamine is our prefe n 1% compound for sta ilizing these lead compounds, the foregoing compounds have been found satisfactory.

There are also a large number-0% commay be used efiectively or the purpose herein described, and these may be obtained by the substitution of various groups such as hydroxy, alkoxy, or amino in the aryl nuclei of the di aryl amines may take place p-hydroxy phenyl- Phenyl-biphenylamine, ONHOO Di biphenylamine, OONHW H:NC NH p-nmino phenyl-a-naphthyla) amine,

o-amino phenyI-b-naphthylamine,

N 2 l-phenylamino-B-amino O naphthalene,

pp-diamino dlphenylwins, HaNONH NH:

Glam

GO 0o @f these compounds, however, phenyl-alpha-naphthylamine represents our preferred embodiment.

lit will he understood, of course, that either tetra ethyl lead or tetra methyl lead may be included in any one of the foregoing illustrative examples. l/7e have found that these solutions so prepared will remain stable indefinitely under the conditions ordinarily employed for the storage of tetra alkyl lead compounds and the compositions containing these compounds.

As many apparently widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not limit ourselves to the foregoing examples or descriptions except as indicated in the following pat m-amino phenyl-a-5-amino naphthylamine,

Biphenyl-a-naphthyb ammo,

blphenylamine, I

ent claims.

X R NHR X i wherein R and R are aromatic hydrocarbon nnclei which may be alike or difierent, and X and X1 are hydroxy, alkoxy, amino groups, or hydrogen.

(mm l 2. The composition of claim 1 wherein, in the formula of the stabilizing compound, at leastone of the R and R represents a phenyl rou I b 3. The composition-of claim ,1 wherein, in the formula of thee-stabilizing compounds, R and R both represent phenyl groups. I

4;. The composition of claim 1 wherein, in the formula ofthe stabilizing compound, X and X both represent OH.

5. The composition of claim 1 wherein, in the formula of the stabilizing compound, at least one of R and R represents a'phenyl group and X represents 0H.

6. A composition comprising tetra alkyl lead having incorporated therewith. phenylalpha-naphthylamine.

.7. The invention of claim 6 in which the tetra alkyl lead is tetra ethyl lead.

9. A composition comprising tetra alkyl lead, hydrocarbons and halogen derivatives of hydrocarbons, and a stabilizing compound having the general formula 9,. The composition of claim 8 wherein, in

the formula of the stabilizing compound, at

least one of the R and R represents a phenyl group.

10. The composition of claim 8 wherein,-in

the formula of the stabilizing compound, it,

and R both represent phenyl groups.

11. The composition of claim 8 wherein, in the formula of the stabilizing compound, X and X both represent @H.

12. The composition of claim 8 wherein, in the formula of the stabilizing compound,at least one of R and R represents phenyl group and X, represents OH.

23. A composition comprising tetra alkyl lead, hydrocarbons and halogen derivatives of hydrocarbons, having incorporated therewith phenyl-alpha-naphthylamine.

1%. The invention of claim 13 in whichthe tetra allryl lead tetra ethyl lead.

15. A composition comprising tetra aikyl lead having incorporated therewith a stabilizing compound comprising a di-arylamine.

16. A composition comprising tetra alkyl lead, hydrocarbons, of hydrocarbons, having incorporated therewith a stabilizing compound comprising a diarylamine.

In testimony tures.

WILLIAM S. ALCQTT.' ALFRED E. PARMELLE.

and halogen derivatives I 

